Color photographic light-sensitive material forming novel cyan images

ABSTRACT

WHEREIN X represents a member selected from the group consisting of a hydrogen atom and a halogen atom; Y represents a member selected from the group consisting of RCONH-, RNHCO-, or RNHCONH; the substituted position of said Y being limited to the mposition and the p-position; R represents an alkyl group having more than 10 carbon atoms; n is an integer of one to two; Y may be the same or different if n is an integer of two, but in this case, if the p-position has been substituted with Y, the other Y has been substituted at the m-position; Z represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a methyl group, a methoxy group and an ethoxy group; and m is an integer one to two; said Z may be the same or different, if n is an integer two. A color photographic light-sensitive material having at least one silver halide emulsion layer containing a cyan coupler of the formula:

United States Patent 1 1 Kishimot o et al.

[ 51 Oct. 23, 1973 [2!] Appl. No.: 190,866

Primary Examiner-Norman G. Torchin Assistant Examiner-R. L. SchillingMion,

Att0rneySughrue, Rothwell, Macpeak vZinn and 57 I ABSTRACT v A colorphotographic light-sensitive material having at least one silver halideemulsion layer containing a cyan coupler of the formula:

wherein X represents a member selected from the group consisting of ahydrogen atom and a halogen atom; Y represents a member selected fromthe group consisting of RCONH-, RNHCO-, or RNHCONH-; the substitutedposition of said Y being limited to the mposition and the p-position; Rrepresents an alkyl group having more than 10 carbon atoms; n is aninteger of one to two; Y may be the same or different if n is an integerof two, but in this case, if the p-position has been substituted with Y,the other Y has been substituted, at the m-position; Z represents amember selected from the group consisting of a hydrogen atom, a halogenatom, a methyl group, a methoxy group and an ethoxy group; and m is aninteger one to two; said Z may be the same or different, if n is aninteger two.

5 Claims, 1 Drawing Figure l. COLOR PHOTOGRAPI-IIC LIGHT-SENSITIVEMATERIAL FORMING NOVEL CYAN IMAGES BACKGROUND OF THE INVENTION 1. Fieldof the Invention This invention relates to a color photographiclightsensitive material having an improved novel cyan color forminglayer containing a napththolic cyan coupler with a long chain alkylgroup, in a silver halide emulsion layer, the said cyan coupler formingthe dye exhibiting an absorption maximum at a wavelength region of 635to 700 nm, when the silver halide emulsion layer containing the cyancoupler is developed with an ordinary color developer containing ap-phenylene diamine as a color developing agent.

2. Description of thePrio'r Art When a color photographiclight-sensitive material having on a support the silver halide emulsion,containing the coupler with an alkyl-substituted phenoxyacetyl group asa well known ballasting oil-solubili'zing group, such as the couplerhaving the following structure (I),

Nncocnio@z-oinn (IE1: H

CONH

- 565 nm in the coupler (II), 625 nm in the coupler (III),

However,a coupler with a long chain alkyl as the balon Q NHCOC'Hz() n inc o macaroni- 3 NH 0 O C11'H:s(n)

(III) and 540 nm in the coupler (IV), respectively. It is clear,however, that these absorption maximum wavelengths are too short forcolor reproduction as a cyan coupler, used for three-color subtractiveprocess and such couplers as mentioned above are not preferable for suchpurpose.

Furthermore, the compound of the following structure (V) having achlorine atom at the coupling position of the coupler (II),

V NBC 0 C Has(n) I s (V) as well as the coupler (II), gives a coloreddye image having an absorption maximum at too short a wavelength sidefor color reproduction and is thus undesirable, as well.

SUMMARY OF THE INVENTION The cyan color image of the color photographiclightsensitive material of this invention has an absorption maximum inthe region of wavelength from 635 to '[00 nm, preferably from 640 to 670nm and is quite preferable in color reproduction.

This invention provides a color photographic lightsensitive material,composed of a red-sensitive silver halide emulsion layer containing anaphtholic cyan coupler with a long chain alkyl as a ballasting group,said cyan coupler giving the color image, having an absorption maximumwavelength at a region of from 635 to 670 nm, preferably from 640 to 670nm, when the silver halide emulsionlayer having the cyan coupler isdeveloped with a color developer with a p-phenylene diamine colordeveloping agent.

DETAILED DESCRIPTION OF THE INVENTION The cyan coupler used in thepresent invention is represented by the following general formula (VI):

Coupler (VIII);

OH @jCONHQ-CONHWHMn Coupler (IX):

ONHCuHuOI) ONH nHaU Coupler (X C ONHCmHu(l1) Coupler (XI):

Coupler (XII):

GQNHQNHCO 0,111,501

Coupler (XIII):

coNHQNacocnHMm CH1 Coupler (XIV):

on 001m o 0 NHQNH c 0 0,111,501) I 00,11.

In addition, among the couplers illustrated above, the coupler having RNHCO- as a ballasting group is more preferable than the coupler havingRCONH-. Wherein, R represents a long chain alkyl group.

The cyan coupler in this invention is used as a solution thereof such asin an ordinary solvent for couplers as dibutyl phthalate, tricresylphosphate, etc. The solvent may also be used together with an auxiliarysolvent, such as ethyl acetate, propyl acetate, etc. The couplersolution is dispersed into a gelatin-containing silver halide emulsionat the state of emulsification by a known way and the photographicemulsion is coated on a support and dried. The binding agent for thegelatin-containing silver halide emulsion may be gelatin alone, orgelatin containing a water-soluble polymer. That is to say, gelatin asthe binding agent may contain a water-soluble polymer; such as polyvinylpyrrolidone or a copolymer of maleic acid and acrylamide, but it ispreferable that at least 50 wt percent of the total binder be gelatin.Also, the support used in this invention may be a transparent film base,such as triacetyl cellulose, polyethylene terephthalate, polystyrene,and the like or an opaque support, such as baryta-coated paper,polyolefin-coated paper, synthetic paper, or an opaque or translucentplastic base.

The light-sensitive material of this invention is colordeveloped by acolor developer containing a p-phenylene-diamine color developing agentand then subjected to the subsequent processings.

The p-phenylenediamine type color developing agent used in thisinvention is preferably a compound represented by the following generalformula (XV), although it is not limited to such compound of the generalformula (XV):

or a salt thereof (XV) wherein R, represents a hydrogen atom or a methylgroup and R, and R represent a lower alkyl group or a substituted loweralkyl group, such as a methyl group, a B-hydroxyethyl group, aB-methylsulfoaminoethyl group, a 4-sulfobutyl group and a butyl group,etc.

Now, the typical examples of the color developing agent having the aboveformula (XV) are shown below, although the said color developing agentof this invention is not limited to these:

0 Compound (XVI) Compound (XVII) C2116 HzNN\ -H2S ot-imo canon Compound(XVIII) /C:H5 I- IzN-N\ 3am s ormo I CzHqNIISO CIIa CH3 Compound (XIX)/C|Hfl(l'l) H2N C|HaSO3H Compound (XX) I /C2H1s H2N N\ -HzSO4 Compound(XXI) /VC2H5 HzNN\ Has 04 zHs In addition, the superior effects of thisinvention become more remarkable by finding proper conditions from suchfactors as the kind of coupler to be used, the manner of producing thelight-sensitive material containing the coupler (such as aratio of theamount of the silver halide emulsion and the amount of thecouplercontaining emulsion, the thickness of the emulsion lected byfiltration to provide -65 g of yellow fine crystals of crudel-hydroxy.-2-N-{[092'- nitrophenyl}]naphthamide having a melting pointof 203205 C. I

2. Preparation of l-hydroxy-2-N-[{2'-aminophenyl}]naphthamide: A mixtureconsisting of 30 g of l-hydroxy-2-N-[{2-nitrophenyl}lnaphthamide. 200 mlof pyridine, and a small amount of 10 percent-palladium carbon wasshaken for 6 hours in a high-pressure vessel at a reaction temperatureof 40 C under a hydrogen pressure of atoms and then the reaction mixturewas filtered and concentrated in vacuo.

The residue was dissolved in a small amount of hot ethanol and cooled,whereby crystals were formed. The crystals thus formed, were collectedby filtration and washed with hot ethanol to provide 10 g of crudelhydroxy-Z-N-(2'-aminophenyl)naphthamide having a melting point of22l-222.5 C.

3. Preparation of1-hydroxy-2-[N-{2-(2,4-di-tertiary.amyl)-phenoxyacetylamino}phenyllnaphthamide(I):

A half amount of the solution of 10 g of 2,4-di-tamylphenoxyacetic acidchloride in 100 ml of acetone was added dropwise with stirring to asolution of 9 g of l-hydroxy-2-N-(2-aminophenyl)naphthamide in 300 ml ofacetone under ice cooling. Thereafter, a 3.3 g of triethylamine wasadded to the mixture and then the remaining acid chloride solution wasadded to the solution followed by stirring for further 20 minutes,whereby an oily product was formed. The reaction mixture was cooled andallowed to stand overnight. The crystals formed were collected byfiltration, dissolved in a 10 percent aqueous potassium hydroxidesolution, and acidified with concentrated hydrochloric acid. The formedcrystals were collected by filtrating, and then I recrystallized from amixture of ethanol and pyridine to layer coated, etc.), andthe kind ofthe color developing agent used. v I

The manner of producingthe couplers of this invention and comparisoncouplers are shown below. First of all, the examples of producing thecompounds (I) and (V), which are the comparison couplers are illustratedbelow.

state, ethanol was added little by little to the product, the coagulatedcrystal was crushed into small pieces, cooled to room temperature,washed with ethanol, and then the yellow crystal was immersed inethanol. After refluxing for about 15 minutes on a steam bath. Thecrystals thus managed, were colprovide 8 g of the coupler (I) appearingas colorless crystals having a melting point of l68-l7l C.

Elementary analysis as C I-l O N Calculated C.- 76.10% H: 7.25% Found c;75.75% H: 7.33%

Synthesis 2 1-hydroxy-4-chloro-2[N-(stearoylamino)phenyllnaphthamide(V):

A half amount of a cooled solution of l l g of strearoyl chloride in 30ml of acetone was added dropwise to a solution of 1 l g ofl-hydroxy-4-chloro-2-N-(2'- aminophenyl)naphthamide in 300 ml of acetoneunder stirring. Thereafter, 3.7 g of triethylamine and then theremaining acid chloride solution were added to the mixture and thentheresulting mixture was stirred for 50 minutes.

The crystals formed were collected by filtration. The filtrate wasconcentrated under a reduced pressure and was cooled to form crystals,which were collected by filtration. The combined crystals were washedwith water, dissolved in a mixture of a 10 percent aqueous sodiumhydroxide solution and ethanol (1:1) and acidified with concentratedhydrochloric acid to form crystals. The crystals obtained wererecrystallized from ethanol to provide 6.1 g of the coupler (V) having amelting point of l57.5l58.0'C.

Calculated Found H: 8.l3% H: 8.32%

Now, the procedures for obtaining the typical couplers (VII), (VIII),(X), and (XII) described above are shown below.

Synthesis 3 l-Hydroxy-2-[N-(3-N-n-hexadecylcarbamoyl)-pheny1]naphthamide (VII):

1. Preparation of m-nitrobezoyl cetylamide:

In the presence of 19 g of triethylamine, 35 g of mnitrobenzoyl chloridewas reacted with 50 g of cetylamine in acetone.

After the reaction mixture was concentrated, the crystals formed werecollected. The crymtals were recrystallized from ethanol to give 62.5 gof mnitrobenzol cetylamide appearing as colorless flaky crystals havinga melting point of 9495 C.

Elementary analysis:

Calculated C: 70.80% H: 9.74% Found C: 70.69% H: 9.68% 2. Preparation ofm-aminobenzoyl cetylamide:

62.5 g of m-nitrobenzoyl cetylamide was dissolved in 140 ml of ethanoland the solution was hydrogenated for one hour at 50 C under hydrogenpressure and palladium-carbon catalyst with stirring. While the reactionmixture was in a hot state, it was filtered to remove the catalyst andthe crystals obtained were recrystallized from ethanol to provide 40 gof the above compound having a melting point of 78 C.

Elementary analysis:

Calculated c: 76.70% H: 11.11% N: 7.78% Found c: 76.76% H: 11.14% N:7.49%

3. Preparation of1-hydroxy-2-[N-(3-N-n-hexadecylcarbamoyl)-phenyl]naphthamide (VI I):

A mixture of 40 g of m-aminobenzoyl cetylamide and 29.5 g ofl-hydroxy-Z-naphthoic acid phenyl ester was heated for 3 hours at l70l80C in an oil bath under reduced pressure and then the reaction productwas recrystallized from ethanol to provide 43 g of the objectivematerial having a melting point of l4l-l41.5 C.

Elementary analysis:

Calculated C: 77.03% H: 8.68% N: 5.29% Found C: 77.19% H: 8.40% N: 5.39%

Synthesis 4 l-Hydroxy-Z-[N-(4'-n hexadecylcarbamoyl)- phenyllnaphthamide(VIII):

By a similar method to that of Synthesis 3, the coupler (VIII) could bereadily produced with a good yield. By recrystallizing the crude productfrom ethanol, 45 g of the colorless crystals of the coupler (VIII)having a melting point of 162 C was obtained.

Elementary analysis:

Calculated c: 77.03% H: 8.68% N: 5.29% Found c: 77.20% H: 8.67% N: 5.01%

Synthesis 5l-Hydroxy-2-[N-(2'-methoxy-5-nhexadecylcarbamoyl)phenyl]naphthamide (X):

24 g of 3-amino-4-methoxybenzoyl cetylamide was heated with an equimolaramount of l-hydroxy-Z- naphtoic acid phenyl ester by same manner as inSynthesis 3 and the coupler (X) could be obtained readily with a goodyield.

By recrystallizing from ethanol, light brown crystals having a meltingpoint of 92l02 C were obtained. Further recrystallization of the aboveproduct from ethanol, gave 14.5 g of the coupler (X) appearing as acolorless crystal having a melting point of 108 C.

Elementary analysis:

Calculated C: 75.00% H: 8.57% N: 5.00% Found C: 74.89% H: 8.79% N: 5.24%

Synthesis 6 Elementary analysis:

Calculated Found A better understanding of the present invention will begained from the following examples, which are simply illustrative andnot limitative of the present invention.

Example 1 3.9 g of l-hydroxy-2-[N-(3-n-hexadecylcarbamoyl)-phenyl]-naphthamide (VII) was dissolved in a mixture of 5 ml oftricresyl phosphate and 5 ml of ethyl acetate as an auxiliary solventand the solution thus obtained as dispersed by emulsification in 50 g of10 percent aqueous gelatin solution in the presence of analkyl-benzensulfonate type surface active agent. 23 g of the preparedemulsion was added to g of a silver iodo-bromide emulsion that had beenpost-ripened.

The smulsi on was coated on a film base by an ordinary manner and dried.The light-sensitive film was light-exposed and developed for 5 minutesin a developing solution having the following composition:2-methyl-4-[(N-B-hydroxyethyl-N-ethyl)I- aminoaniline sulfate (XVI) 2.5g Anhydrous sodium sulfite 2.0 g Sodium carbonate (monohydrate) 82.0 gPotassium bromide 2.0 g

Water was added up to 1,000 ml.

Potassium ferricyanide Potassium bromide Water was added up to 1,000 ml.

The film was washed with water for 10 minutes and fixed in a bath havingthe following composition:

Sodium thiosulfate Water was added up to 1,000 ml By washing thephotographic film with water and then drying it, a sharp blue-greenimage having an abf I a 3,767,411

sorption maximum at 655 nm and less unnecessary absorption was obtained.

I BRIEF DESCRIPTION OF THE DRAWING EXAMPLE 2 .color developing agent(XIX) instead of the colordeveloping agent (XVI) in Example 1 andsubjected to the subsequent processings as in Example I to provide asharp blue-green image having an absorption maximum at 650mm.

EXAMPLE 3 A photographic light-sensitive film was prepared by the sameprocess as in Example 1 using the coupler (IX) instead of the coupler(VII) used in Example 1. After light exposure, the photographic film wasdeveloped in a color developing bath having the same composition as thatof Example 1, except that the color developing agent (XXI) was usedinstead of the color developing agent (XVI) and then subjected to thesubsequent processings as in Example 1 to provide a sharp blue-greenimage having a spectral absorption maximum at 650 nm.

EXAMPLE 4 A photographic light-sensitive film was prepared by the sameprocedure as in Example 2 using the cyan coupler (X). After lightexposure, the photographic film was developed in a color developingsolution having the same composition as that of Example 2, except thatthe color developing agent (XVII) was used in place of the colordeveloping agent (XIX) and then subjected to the subsequent processingsas in Example 1 to provide a sharp cyan color image having a spectralabsorption maximum at 692 nm.

EXAMPLE 5 The same film as used in Example 4 was developed in thedeveloping bath having the same composition as that in Example 4, exceptthat the color developing agent (XVIII) was used in place of thecolordeveloping agent (XVII) and then subjected to the subsequentprocessings as in Example 1 to provide a sharp cyan color image havingthe spectral absorption maximum at 696 EXAMPLE 6 A photographiclight-sensitive film was prepared by the same manner as in Example 1,except that the coupler (XIV) was used in place of the coupler (VII).After light exposure, the film was developed in a developing bath havingthe same composition as in Example 1, except that the color developingagent (XX) was used in place of the color developing agent (XVI) andthen subjected the subsequent processings as in Example l to provide acyan dye image having the spectral absorption maximum at a longerwavelength region of 684 nm.

DETAILED DESCRIPTION OF THE DRAWING The example of the cyan color imageproduced by the photographic light-sensitive image of this invention isshown as the curve (1) in the FIGURE and the absorption maximum of thecyan color image was at 655 nm. This value isparticularly suitable forcolor positive films, color reversal films and color papers, but it isclear that the spectral absorption curves of the cyan color imagesforming from the comparison examples, shown by the curve (2) and thecurve (3) in theFIG- URE are not preferable for the purposes of colorpositive films and the like. In particular, as shown by the curve (2),the spectral absorption curve of a color image obtained from the couplerII having the long chain alkyl group as the ballasting group illustratesclearly that the absorption maximum is in the shorter wavelength side,to make it difficult to obtain correct color reproduction. Also, it hasbeen confirmed that a desirable absorption pattern cannot be obtainedthroughout the whole region, even if the ratio of the color and thesilver halide and the kind of the color developing agent are varied.

The color photographic light-sensitive material of this invention ischaracterized by using l-hydroxy-Z- naphthanilide type cyan couplerhaving a long chain alkyl group as a ballasting group and provides acolor image having an absorption maximum at the wavelength regions of635-700 nm, and a sharp curve of spectral absorption for cyan color,which is not expected by an ordinary technique. Usually, the absorptionmaximum of a color image formed by using a lhydroxy-2-naphthanilide typecyan coupler having an oil solubilizing group is at a wavelength regionlonger than 700 nm as shown by the curve (3) in the FIGURE. On the otherhand, a color image in a case of using a l-hydroxy-2-naphthanilide typecyan coupler having a long chain alkyl group as the ballasting group hasan absorption maximum or excess absorption in a shorter wavelengthregion than 630 nm or shows absorption in a region of longer than 700nm, a wide absorption curve near the range of absorption maximumwavelength, or much undesirable absorptions, which make the use of sucha cyan coupler undesirable. These examples are shown as the curve (2) inthe FIGURE mentioned above and reported by Hans I-I. Credner in the textdescribed before.

As mentioned before, the spectral absorption character of the cyan dyeimage by the photographic lightsensitive material of this invention,such as being present in a region of 635-700 nm in the absorptionmaximum wavelength, is suitable for the cyan coupler, using a red-lightsensitive silver halide emulsion layer, of color positive film, colorreversal film, and color paper.

Moreover, the cyan coupler used in this invention can be easily producedwith a low cost.

Although the present invention has been adequately described in theforegoing specification and examples included therein, it is readilyapparent that various changes and modifications can be made withoutdeparting from the spirit and scope thereof.

What we claim is:

l. A color photographic light-sensitive material having at least onesilver halide emulsion layer containing a cyan coupler represented bythe following general formula, said cyan coupler giving a cyan colorimage having the absorption maximum wavelength at 640-670 nm when theemulsion layer is colordeveloped by a color developer containing apphenylene diamine type color developing agent:

at the m-position; Z represents a member selected from the groupconsisting of a hydrogen atom, a halogen atom, a methyl group, a methoxygroup and an ethoxy group; and m is an integer of one or two; said Z maybe the same or different if n is an integer two.

2. The color photographic light-sensitive material of claim 1, whereinsaid p-phenylenediamine type color developing agent or salt thereof isrepresented by the formula:

wherein R represents a member selected from the group consisting of ahydrogen atom and a methyl group; R and R represent a member selectedfrom the group consisting of an alkyl group having one to four carbonatoms, a B-hydroxyethyl group, a B-methylsulfoaminoethyl group and a4-sulfobutyl group.

3. The color photographic light-sensitive material of claim 1, whereinsaid cyan coupler is:

and said p-phenylenediamine type color developing agent is:

4. The color photographic light-sensitive material of claim 1, whereinsaid cyan coupler is:

C O NHC raHas @jCONHQ and said p-phenylenediam ine type color developingagent is:

5. The color photographic light-sensitive material of claim 1, whereinsaid cyan coupler is:

C ONHCmHu(n) and said p-phenylenediamine type color developing agent is:

CaHs

HaN N H2804

2. The color photographic light-sensitive material of claim 1, whereinsaid p-phenylenediamine type color developing agent or salt thereof isrepresented by the formula:
 3. The color photographic light-sensitivematerial of claim 1, wherein said cyan coupler is:
 4. The colorphotographic light-sensitive material of claim 1, wherein said cyancoupler is:
 5. The color photographic light-sensitive material of claim1, wherein said cyan coupler is: